Conversion of hydrocarbon oils



Patente d' Aug. 7, 1945 UNITED STATES PATENT oer-ice CONVERSION OF HYDROCARBON OILS Aristid V. Grosse and William J. Mattox, Chicago,

Ill., ,assignors to Universal il Products Com-.

pany, Chicago, 111., a corporation of Delaware No- Drawing.

This invention relates to the conversion of hydrocarbon fractions produced in distilling petroleum oils and especially those of a distillate character which are vaporizable without substantial decomposition.

In a more specific sense the invention is concemed with a modification of hydrocarbon oil conof what catalysts to employ when-cracking differ-- ent fractions from different petroleums is largely empirical and admits of no generalizations. A large number of the catalysts developed'for cracking have a tendency to accelerate reactions leading to the formation ofgas rather than of gasoline, this being particularly evidenced by reduced metal catalysts such as nickel or iron and many of such catalysts are sensitive to sulfur poisoning and are quickly coated with carbonaceous materials which render them practically inert. This deposition of carbonaceous materials is many times related to the type of decomposition reactions .selectively fostered by the catalyst and in general it may be said that very few, if any, catalysts which have been tried thus far in cracking reactions have reached a commercial status. The

present invention is concerned with the use of catalytic materials which are specially adapted to Application August 18, 1939, Serial No. 290,847

' 2 Claims. (01.196-52) and by their ease and simplicity of manufacture and their exact reproducibility.

In one specific embodiment the present invention comprises a process for producing gasoline by subjecting higher boiling hydrocarbon oils at a temperature in the approximate 'range of 500-700 C. to contact with a granular catalytic material comprising a mass formed by calcining an alkali metal-free composite of a major proportionof precipitated silica hydrogel and a minor amount of precipitated chromium hydroxide hydrogel,

In the following specification the terms silica and "chromia are used in a broad sense. -Th'e chromia is used in referring to chromium sesquioxide or a hydrated chromium hydroxide which forms chromium sesquioxide on calcination. Inasmuch as the chemical knowledge of the solid state has not been developed perfectly, it is not possible to give the structure of all solid substances. All that can be said definitely concerning these masses is that they contain silicon, oxygen, and chromium; Generally speaking, however, the oxides mentioned show more or less low catalytic activity individually but in the aggregate display high activity. This activity is not an additive function, it being relatively constantefor a wide range of proportions of the components, whether accelerate the cracking of heavy fractions of petroleum and other hydrocarbonaceous materials .to increase the rate of production of gasolineboiling range fractions. The preferred'catalysts are characterized by selectivity in accelerating gasoline-forming reactions rather than gas-form ing reactions, by their refractory character which enables them to retain their catalytic properties through many repeated periods of use and reactivation under severe conditions of temperature,

in molecular or fractions of molecular proportions. Neither component can be. determined as the one component for which the other may be considered as the promoter according to conventional terminology, nor can one component be determined as the support and the other the catalyst proper.

According. to the description of the preparation of the preferred catalysts given below, precipitated chromia hydrogel is composited with silica hydrogel and then the composite is washed, dried, formed into particles, and calcined; or the composite may be washed, formed into particles, dried, and then calcined to produce a catalytic mass. However, the different catalysts which may be so produced may not necessarily give equivalent results in service.

According to the. present invention the heavier distillate fractions of petroleum are cracked at a temperature in the order of 500- 700 (7., and at substantially atmospheric pressure, or at an increased pressure, while in contact with catalysts produced preferably by precipitating-chromia h'ydrogel upon a relatively pure salt-free silica hy- I cordancewith the I to employ silica which has been prepared by precipitation as a hydrogel.

v tory silica gel is to acidify the wet condition silica hydrogel may be suspended in and boiled with a solution of a chromium salt such as, for example, an aqueous solution of chromium ni-.

drogel, followed by washing to remove water soluble salts and then drying to remove a major portion of the combined or adsorbed water. A superatmospheric pressure up to approximately 70 atmospheres may also be employed for the cracking of such hydrocarbon distillates. V v

The finished catalysts prepared as indicated. above, may'contain approximately 2-35%, by weight of chromia, although as a rule. preferred compositions for these catalysts based upon yields and quality of gasoline are in the range of 4-10% chromia. These proportions will-vary considerably wi'th the particular hydrocarbon fractions subjected to catalytic cracking and with the degree of conversion desired in any particular case.

It is to be recognized that very little is known positively concerning the mechanism of enhanced activity of complex catalysts and no attempt will be made herein to ofier any definite reasons for the observed mutually promotional effects of silica and chromia composites prepared for catalytic cracking purposes according to the present invention. There may be a catalytic effect due to the compositing of the catalyst components and it may be that the chromia is the more active catalyst and is dispersed extensively in and on the silica in order to present a large surface.

In manufacturing the preferred catalysts in acpresent process it is necessary cipitation from solution as a hydrogel within or deposited also by prei upon which the chromia is The most convenient and ordinary method of preparation of a satisfacan aqueous solution of sodium silicateby the addition of the required amount of hydrochloric acid. The excess of acid and the concentration of the solution in which the precipitation is brought about will determine the eventual primary activity of the silica and its suitability for compositing with the chromia hydrogel to producea catalyst of high activity. In general, the most active silica is produced by adding only enough acid to cause gel formation to occur in the sodium silicate, but the material formed at such a point is rather gelatinous and is filtered with difliculty. Further, the silica hydrogel is coagulated incompletely at this point. By adding a moderate excess of acid after the hydrogel has formed, the desirable physical characteristics in regard to catalyst activity are conserved while the material'is made more suitable for filtration and the silica hydrogel is precipitated more completely. Fairly good hydrated silica for present catalytic purposes may be made by employing as high as 20% excess hydrochloric acid by the addition of more acid, but beyond this Point a part of the more desirable properties is lost. After precipitating the silica gel it is preferably washed until substantially free from salts by using several alternative reagents, which will be described later.

In one mode of preparing the activated form, the silica hydrogel may be boiled either with separately precipitated chromia, which is added in to the silica suspension, or the trate. In either case thefinal precipitate comprising essentially the hydrogels of silica and chromia is finally washed to substantially complete removal of water soluble materials, and dried at about 100-125 C; for 2-6 hours to produce a rather crumbly and granular material containing approximately 15-30% moisture, which may be ground and pelleted or sized to produce particles of catalysts. Alternatively, the washed composite of silica and chromia hydrogels may beformed into particles, then dried and calcined to produce the active catalyst. For this calcination a temperature is employed in the approximate range of 500-1000 C. The temperature of calcinatiqn has a profound influence upon the properties of the finished catalyst. Use of a temperature in the lower portion of the range indicated results in the formation of a catalyst with strong dehydrogenating activity, while the employment of a temperature of approximately 1000 C. produces a catalyst of lower dehydrogenating activity, but with high cracking activity for producing a. highly olefinic gasoline.

The necessary chromia hydrogel is deposited preferably in or on washed alkali metal-free silica gel by adding an alkaline precipitant such as ammonium hydroxide, ammonium carbonate, or ammonium sulfide to an aqueous solution of a chromium compound in which previously prepared and washed silica gel is suspended, followed by washing of the total composite precipitate.

As a further alternative method of producing the desired catalyst, a solution of a chromium salt may be added to a solution of an alkali metal silicate to jointly precipitate silica hydrogel with chromia hydrogel and further amounts of silica hydrogel may then be precipitated by the addition of acid. A characteristic equation illustrating the preparation of a silica-chromia catalyst is given below, although in it no account is taken of water of hydration:

It will be obvious that the employment of the reactions shown in the above equation will be limited on account of the molal proportions involved so that such a method of preparation of a composite may need supplementing by the presence of acid for further precipitation of silica to obtain the desired ratio.

It should be emphasized in the present connection that the catalysts which characterize the process of the invention are essentially composites ,of substantially pure amorphous silica with amorphous chromia. Experiments have indicated that distinctly inferior catalytic materials are obtained when either the silica or chromia of the composites has crystalline characteristics. That is, it is not suflicient to precipitate chromia on such nat- -materials may be.

ural siliceous materials as powdered quartz 0r diatomaceous earth however finely divided these Similarly, inferior catalysts result if any known forms of crystalline chromia are mixed with carefully prepared and washed amorphous silica. Silica of some value has been obtained by the hydrolysis of silicon tetrachloride, although that obtained similarly from 5111- con tetrafluoride was decidedly inferior.

In the preparation of active silica hydrogels from water soluble silicates, a series of experiments has further indicated that hydrochloric acid is .the best common material to use as a precipitant, although sulfuric acid and other acids give but slightly inferior results. The precipitation is best conducted at approximately normal temperature since tests made at temperatures of the order of C. gave silica gel which was inferior.

I! alkali metal salts arepresent in sufilcient quantities in either the original precipitated silica gel, or inthe final catalyst composite, catalysts are obtained which are not sufficiently active under the usual cracking conditions. If present in smaller quantities, catalysts may be obtained which are active in the early stages of use but lose their activity during the elevated temperatures reached in regeneration by the burning of! of carbonaceous deposits in a stream of air or other oxygen-containing gas. Catalysts which contain still less sodium may be heated to as high as approximately 1000 0. without loss of activity. For these reasons special washes are preferably used which are capabl of removing these sodium compounds from the catalyst so that only quite minute amounts remain, since it has been found that this sodium cannot be washed out by water alone. The washes developed are dilute hydrochloric acid and ammonium chloride, which serve to displace the sodium in the catalyst so that additional water washing can remove the sodium.

For economic reasons hydrochloric acid seems to be preferable to ammonium chloride and also because ammonium chloride seems to be slightly v inferior in its eifectiveness.

Catalysts prepared for the process by the above general procedure evidently possess a large total contact surface corresponding to a high porosity, the pores being of such size that hydrocarbon oil vapors are able to penetrate to a considerable distance and yet not so small that when the pores become clogged with carbonaceous deposits after a long period of service, they are diflicult to reactivate by oxidation. This structure is also retained after many alternate periods of use and reactivation as-evidenced by the fact that catalysts may be reactivated and reused for long periods of time.

According to the present process catalystsprepared by the general procedure described in the preceding'paragraphs are utilized to the best ad-' vantageas'reactorillling materials in the form of. small pellets or granules. In the majority of cases wherein hydrocarbon fractions readily vaporizable at moderatetemperatures without extensive' decomposition are employed,, the average particle size is within the range of 6-10 mesh. which may apply either to small pellets ofunlform size and short cylindrical-shape or to particles of irregular size and shape produced by the grinding and sizing of the partially 'dehydrated materials.

while the simple method of preheating a given fraction of hydrocarbon oil. vapors to a temperature suitable for their cracking in contact with the catalysts and then passing the vapors over a stationary mass of catalyst particles contained 3 ina cylindrical chamber (preferably vertical) may be employed in some cases, it is usually preferable to pass the preheated vapors through banks of relatively small diameter catalyst-containing tubes in multiple connection between heade since this arrangement of apparatus is better adapted to permit exterior heating of the catalyst tubes to compensate for the heat loss .in the endothermic cracking reactions. The

tions amenable to further catalytic cracking, gasoline boiling range materials and fixed gases, the intermediate fractions being returned directly to admixture with the charging stock so that ultimately there is a complete recycling of the unconverted fractions and maximum utilization of the cracking stock for gasoline production.

As the activity of the catalyst for producing gasoline decreases with use and is highest when 10 fresh or freshly reactivated, this invention is carried out preferably by utilizing cracking reactors in duplicate so that the cycle of operation may consist of alternate periods of cracking and of reactivation by burning off the carbonaceous deposits in an atmosphere of an oxygen-containing gas. 7 Powdered catalyst which has become spent by use may be withdrawn from and reactivated outside of the cracking system, after which it may be returned to the cracking reactors with the oil undergoing conversion.

The present process besides being characterized by ,the use of novel catalysts of relatively long life is further characterized by the production of good yields of high anti-knock gasoline,

with relatively low gas formation.

In the cracking of petroleum distillates of the nature of gas oil at a temperature in the range of 500-700 C. the liquid space velocity employed is adjusted to the cracking temperature used in order toproduce a relatively high yield of gasoline with low formation of gas and small deposition on the catalyst of carbonaceous materials. Thus for cracking at approximately 500 C. the preferred liquid space velocity is in the range of 0.2-20; at

550-600 c.,. o.5- 5 and at-650 c., 20-100, the

liquid velocity being the volume of oil charged hourly per volume of catalyst space in the reactor. The times given catalyst is used before reactivation will vary with they operating conditions and rapidity of carbon deposition. This duration of the cracking period may be in the range of 0.5-20 hours, but is preferably approxi- -'matelyii hours. because of the deposition thereon of carbonaceous 4,5 materials are reactivatedat' the cracking tem-- perature by treatment with air or another oxygencontaining gas. During this reactivation treatment'the catalyst temperature may increase to approximately 650 C. because of the heat of combustion of the carbonaceous material. Af

ter reactivation, the catalyst has approximately the same activity for promoting cracking as when fresh.

The following examples of the preparation and use of catalysts peculiar to the present invention are given to indicate the novelty and utility in the present process, although not with the purpose of limiting the invention in exact agreement with the data introduced.

EXAMPIE 1 For use in the preparation of the preferred cracking catalyst, a silica hydrogel obtained by precipitation from sodium silicate solution with dilute hydrochloric acid was washed with distilled water, dilute amonium chloride solution, and finally with distilled water until the water wash was free from sodium compounds, as shown by test with magnesium uranyl acetate solution.

The undried gel, containing 84.2% water and corresponding to 311 parts by weight of silica. was suspended in 14,000 volumes of distilled water and 142 parts by weight of chromium nitrate nona-hydrate dissolved in 400 volumesof water was added with vigorous stirring. Ammo- Catalysts havin low activity I atalyst cont 8% omia in comparison with 16.3 and 17.0% by e presence of catalysts containing 4 and 32% chromia, prespectively. ed and dried to TABLI2 ground to pass a mesh of silica-chromia cracking catalyst 2,881,820 0.1) was then added was obtained with the 0 slowly until the precipitation of chromium hychr solution volume of gasoline produced in th of pret a hydrogels was se by weight 01' hydrogen- Efiect of chromia concentration on the activity ormed into 3 x 3 mm. pelleting machine. The 10 n oven at 200 C. for two Chmmmm nium hydroxide (7 Norm droxide hydrogel was complete and the was alkaline to litmus. The composite cipitated silica and chromi arated by filtration, wash moisture content, then screen, admixed with 7 ated cocoanut oil and f pellets by means of a pellets were dried in a 1 1 e 0 .13 4 0. a. M ea 1 121 c %ww 1M 5 000 III m at m m m m W0. we 03 0 m m s m tsfissmmu a m 505 n C m 0 W Ufl 0 0 0 7 w 0 8 a a e%b & ml I n w an 1 u nods o u n m b s T m n" 3 mo %.u no m mm 0 m eeh T i I n m rcc 3 t w 8. m e .m u n F. p m m I im um m" m mw L a 1m" nm eh m h m md n 1w I mv w m mm I" m pwam T m Qmmm mum. u.. m or T; em n n cm m m qm mm n "m" a" ew umm n mmm. um um uwmybum I u b n men. U m" m n it nw n m m ZP u .1 10... Nina m whats: a t t u w mmw marmm ma m n. "mi ummmmmm I m mu s m mmu m m m mmtmmmm m Hm "h wm m amm 0 1n w Iim l en n..fl .Ibm HIDE-P... ae. n m H n w s mwjawed umm mmaan em m d iu ipmmm a ra Mm mwe mm mmmm h df m el e nnn I .m r .1 8 0 m m I w. .Um mmwmmmmmhmmmmmmw .m mmmmmL1mw mmEPPP Wa M t a m mubm m wm w rs Bu .e oo n eo e a l 0 u w M. cam mmwommmunmmnmmmmmcmwmMms mm w mr ono c w. w m m A m vsam E o m n a o w m a a c. n. w 0 V w t 0 06401.0 3 .0.0 assist stan a we n 4% m m m m m W M ww5m2l uwm u pl mm-MIN llw-fl3mmlfi c a mw a m c m m m 30 iii 1 .00 imam r n m d. nmmm m $1002 3m mama W 0 0 1 0 m or m m m m e m 011210 0 3 se weed t hmww 0 mi .mcwn m 5 MRLZOJ. 0ww %4 MWMNIBO RWMII M13 8, .f. S a h a mfi n m 1 s 8 WM r l fl uum H m h" an: mm m m m m m" m mm mwumdf w mmw 1 mu m m m m eo o h 7 9.1 H m u m m m e m m a im m m .m Wa .mbumerywce u mm in m. m mmht so mw bgu T ah 1m m a L a a n .ww I L m u e e a 7 id h r um m Wm mm ww Hr m E m mw dt e e8. r n Iw" e" "mu "n "em, e .n n. Hi c r n 1 T in um" nd mnn n m m mm mm mm mm um bm:m a" mmmwwmmwm a f a mn w D. C t i fi "n" .w. n l. 0 o h S 0 0D 0m m 0s 6 m t n. r.ltf% .a 8 w .W d mw m. MaB Cr k shem iad Iwhfme. w l mu o m wm aotp d a m mm mmn ur mm mmnrzmem m 0 m e a b ah ym d o n ttfidcuoaoms m m mwmm mflmm P .0 0e mmnt e .r m mn w ss mw m +m anh00+ r 00mm mm m mmnmw mmmw mmmwmw wmmdnhmmmdwfimmfiemwimmMoE o n. r r r n n f h3Cmm mlmw v d m C TTP A A P These results show that the gasoline yields 05 were higher and gas 1 s less .with the catalyst Also, from the hydrogen dent that the catalyst perature had a lower and a lower carbon and its seen from the precednumerical data presented,

on is intended to be unduly formation observed it is evi calcined at the higher'tem dehydrogenatlng activity 1 hour forming tendency. gas oil on The character of the present invention novelty and utility can be specification and ough neither secti by volume limiting in its generally broad scope.

calcined at 1000 C.

alth EXAMPLE 2 Chromia-silica catalysts containing 4, 8, and 32% by weight 01. chromium sesquioxide were prepared from washed silica gel by the same procedure as described for preparing the ca st used in-Example 1, with additional calcination for 10 hours at 1000 C. Cracking runs of duration were made on Pennsylvania these catalysts in quartz tubes at 550 C. under 2 show that a gasoline yield of 23.1

2. A pr for producing gasoline from jecting the heavier hydrocarbon oils which comprises subheavy oil to cracking conditions in the presence. of a cracking catalyst comprising precipitated silica. gel and precipitated chromia.

5 gel, said ca mine and taiyst being substantially free oi aluaikali metal compounds. 

